Ultra-small molecule-like Au_N nanoclusters made by a number of atoms N less than 30 were produced by ion implantation in silica substrates. Their room temperature photoluminescence properties in the visible and near-infrared range have been investigated and correlated with the Er sensitization effects observed in Er–Au co-implanted samples. The intense photoluminescence emission under 488 nm laser excitation occurs in three different spectral regions around 750 nm (band A), 980 nm (band B) and 1150 nm (band C) as a consequence of the formation of discrete energy levels in the electronic structure of the molecule-like Au_N nanoclusters. Indeed, energy maxima of bands A and C scale with N^−1/3 as expected for quantum confined systems. Conversely, the energy maximum of band B appears to be almost independent of size, suggesting a contribution of electronic surface states. A clear correlation between the formation of band B in the samples and Er-related photoemission is demonstrated: the band at 980 nm related to Au_N nanoclusters resonant with the corresponding Er³⁺ absorption level, is suggested as an effective de-excitation channel through which the Au-related photon energy may be transferred from Au nanoclusters to Er ions (either directly or mediated by photon absorption), eventually producing the Er-related infrared emission at 1540 nm.